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In limited cases, the reaction of metal acetylide with amino aldehydes proceeds in a highly stereoselective manner. For example, see: (a) Garner, P.; Park, J. M. J. Org. Chem. 1990, 55, 3772.
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note
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We observed isomerization of the 2,3-trans-2-ethynylaziridine 11b into the corresponding 2,3-cis-isomer 10b under the aziridination conditions (NaH, DMF, room temperature). Although a prolonged reaction time (> 10 h) was required for an efficient conversion (cis:trans = >95:5), equilibration of the products would be one of the important factors for the cis-selective aziridination. Thermodynamic preference of the related 2,3-cis-aziridines over their trans-isomers is well documented by our previous study; see: ref 2g.
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For a methanesulfonic acid mediated ring-opening reaction of vinylaziridines, see: (a) Tamamura, H.; Yamashita, M.; Muramatsu, H.; Ohno, H.; Ibuka, T.; Otaka, A.; Fujii, N. Chem. Commun. 1997, 23, 2327.
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(b) Tamamura, H.; Yamashita, M.; Nakajima, Y.; Sakano, K.; Otaka, A.; Ohno, H.; Ibuka, T.; Fujii, N. J. Chem. Soc., Perkin Trans. 1 1999, 2983.
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Tamamura, H.1
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Ohno, H.6
Ibuka, T.7
Fujii, N.8
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